JP2019173254A - Paper or paper board containing cellulose nanofiber - Google Patents

Abstract

To provide high strength paper or paper board containing waste paper pulp without deteriorating tone.SOLUTION: There is provided paper or paper board containing waste pulp of 20 wt.% or more, in which at least one paper layer contains a cellulose nanofiber of 3 to 10,000 wt.ppm based on the pulp of the paper layer.SELECTED DRAWING: None

Description

  The present invention relates to paper or paperboard containing cellulose nanofibers.

  In general, paper and paperboard are delivered to the user through printing, various processing, and the like, and the strength of the paper and paperboard is often required in the process. As paper with improved strength, high-quality paper containing mechanical pulp (Patent Document 1), paper added with a paper strength improver, and the like are known. In recent years, addition of cellulose nanofibers has been studied to reinforce the effect of the paper strength improver (Patent Document 2). However, since the technique described in Patent Document 1 contains a large amount of mechanical pulp, there is a problem that the formation of paper tends to deteriorate. Moreover, the technique described in Patent Document 2 is a study on paper using high-quality pulp that is relatively easy to obtain strength. On the other hand, the strength improvement about the paper or paperboard which used many used paper was calculated | required.

JP 2005-336678 A Japanese Patent Laid-Open No. 2006-166444

  The inventors of the present invention have found that when a large amount of cellulose nanofiber is added to improve the strength, the formation is lowered, and this tendency is remarkable in paper or paperboard containing waste paper pulp. In view of such circumstances, an object of the present invention is to provide high-strength paper or paperboard containing waste paper pulp without damaging the formation.

Inventors solved the said subject by containing a cellulose nanofiber. That is, the said subject is solved by the following this invention.
(1) Contains 20% by weight or more of waste paper pulp,
Paper or paperboard, wherein at least one paper layer contains 3 to 10,000 ppm by weight of cellulose nanofibers relative to the pulp of the paper layer.
(2) Paper or paperboard as described in (1) whose said cellulose nanofiber is carboxylated cellulose nanofiber.
(3) The paper or paperboard according to (1) or (2), wherein the cellulose nanofiber is a carboxylated cellulose nanofiber obtained by oxidation using an N-oxyl compound.
(4) The paper or paperboard according to (1), wherein the cellulose nanofibers are carboxymethylated cellulose nanofibers.
(5) The paper or paperboard according to any one of (1) to (4), wherein the waste paper pulp is selected from the group consisting of undeinked waste paper pulp, deinked waste paper pulp, and combinations thereof.
(6) The paper or paperboard according to any one of (1) to (5), wherein the waste paper pulp is magazine waste paper pulp.
(7) The paper or paperboard production method according to any one of (1) to (6),
A method for producing paper or paperboard, comprising a step of papermaking a pulp slurry containing waste paper pulp and cellulose nanofibers.

  According to the present invention, high-strength paper or paperboard containing waste paper pulp can be provided without damaging the formation.

  Hereinafter, the present invention will be described in detail. In the present invention, “X to Y” includes X and Y which are the end values.

1. Cellulose nanofiber-containing paper or paperboard The paper or paperboard of the present invention contains a specific amount of waste paper pulp and cellulose nanofiber (hereinafter also referred to as “CNF”). The paperboard generally refers to a particularly thick paper, but in the present invention, for example, a cardboard base paper, a paperboard base paper, a white paperboard, a chipboard, a yellow ball, a paperboard base paper, a carrier tape, a multilayer paper such as a “paperboard” Single-layer paper is called “paper”. The paper or paperboard of the present invention contains cellulose nanofibers in at least one paper layer.

(1) Paper layer Paper that is a single-layer paper includes one paper layer that uses pulp as a main material, and paperboard that is a multilayer paper includes a plurality of paper layers that use pulp as a main material. The paper layer in the paperboard is preferably two or more. For example, in the case of two layers, “surface layer” “back layer”, in the case of three layers “surface layer” “middle layer” “back layer”, in the case of four layers “surface layer” “ In the case of 5 layers, it consists of “surface layer”, “surface layer”, “middle layer”, “surface layer”, and “surface layer”. In the case of five or more layers, any of the five layers may be a plurality of layers, but the middle layer is preferably a plurality of layers. The prescriptions for each layer may be the same or different, but any two or more of the paper layers may be the same prescription.

  In the present invention, waste paper pulp is used as the raw material pulp. Examples of the raw material for waste paper pulp include those derived from paper such as newspaper waste paper, cardboard waste paper, high-quality waste paper, magazine waste paper, unprinted waste paper, and discarded confidential documents. The waste paper pulp may be undeinked waste paper pulp or deinked waste paper pulp. Among these, undeinked waste paper pulp is preferable, and undeinked magazine waste paper pulp is more preferable from the viewpoint that the effect of improving paper strength can be expressed at a higher level. Other pulps are not particularly limited, and examples include hardwood-derived pulp, softwood-derived pulp, and non-wood pulp. The paper or board of the present invention contains 20% by weight or more of waste paper pulp in the whole pulp (absolutely dry). The paper layer in which the waste paper pulp exists is not limited, and may be present in all paper layers or may be present in a specific paper layer. The lower limit of the waste paper pulp content is preferably 40% by weight or more, more preferably 60% by weight or more, and still more preferably 90% by weight or more. The upper limit is not limited and may be 100% by weight, but is preferably 98% by weight or less.

(2) Cellulose nanofiber (CNF)
The content of CNF is 3 to 10,000 ppm by weight with respect to the pulp (absolutely dry) in the paper layer. In the present invention, CNF is different from pulp. When the paper layer contains CNF, the strength of paper or paperboard containing waste paper pulp can be improved. From this viewpoint, the lower limit of the CNF content is preferably 5 ppm by weight or more, and more preferably 10 ppm by weight or more. A preferable upper limit is 8000 ppm by weight or less, 5000 ppm by weight or less, 1000 ppm by weight or less, 500 ppm by weight or less, or 100 ppm by weight or less. Since CNF is highly effective in retaining moisture, if the amount of CNF added exceeds 10,000 ppm, the drainage of the pulp slurry may deteriorate and the papermaking speed during production may not increase. There is a risk that the moisture will be too high and the strength of the paper will decrease. The inventors have found that by adding a relatively small amount of CNF to a pulp slurry containing 20% by weight or more of waste paper pulp, a high paper strength improvement effect can be obtained without greatly changing the physical properties of the pulp slurry.

  CNF is a single microfibril of cellulose having an average fiber diameter of 2 to 200 nm and an average fiber length of 0.1 to 5 μm obtained by defibrating a cellulose-based raw material. The average fiber diameter of CNF used in the present invention is preferably about 4 to 100 nm, and the length is preferably about 0.2 to 1 μm. The average fiber diameter and average fiber length of CNF are obtained by averaging the fiber diameter and fiber length obtained from the observation results of each fiber using an atomic force microscope (AFM) or a transmission electron microscope (TEM). It is done.

  As CNF used by this invention, the CNF manufactured by carrying out the chemical | medical modification after cellulose-denatured raw material may be used, and the CNF manufactured only by the mechanical fibrillation without performing chemical modification may be used. Chemical modification is not limited, and examples thereof include oxidation, etherification, phosphorylation, esterification, silane coupling, fluorination, and cationization. Of these, oxidation (carboxylation) or etherification (carboxymethylation) is preferred. Hereinafter, the chemical modification will be described using carboxylation and carboxymethylation as examples.

1) Cellulose raw material Cellulose-based raw materials are not particularly limited, and kraft pulp or sulfite pulp derived from various woods, powdered cellulose obtained by pulverizing them with a high-pressure homogenizer, a mill, or the like, or purified by chemical treatment such as acid hydrolysis. Microcrystalline cellulose powder or the like can be used. In addition, plants such as kenaf, hemp, rice, bagasse and bamboo can also be used. Among these, bleached kraft pulp, bleached sulfite pulp, powdered cellulose, and microcrystalline cellulose powder are preferable, and powdered cellulose and microcrystalline cellulose powder are more preferable.

Powdered cellulose is a rod-like particle made of microcrystalline cellulose obtained by removing a non-crystalline portion of wood pulp by acid hydrolysis, and then pulverizing and sieving. The degree of polymerization of cellulose in the powdered cellulose is preferably about 100 to 500, the degree of crystallinity of the powdered cellulose by X-ray diffraction is preferably 70 to 90%, and the volume average particle size by a laser diffraction type particle size distribution measuring device. Is preferably 100 μm or less, more preferably 50 μm or less. When the volume average particle diameter is 100 μm or less, a cellulose nanofiber dispersion excellent in fluidity can be obtained. As the powdered cellulose used in the present invention, for example, a fixed particle size in the form of a rod shaft produced by a method in which an undegraded residue obtained after acid hydrolysis of a selected pulp is purified and dried, and pulverized and sieved. A crystalline cellulose powder having a distribution may be used, or commercially available products such as KC Flock ^R (manufactured by Nippon Paper Chemicals Co., Ltd.), Theolas ^TM (manufactured by Asahi Kasei Chemicals Co., Ltd.), and Avicel ^R (manufactured by FMC) may be used. .

2) Oxidation (carboxylation)
Oxidation can be carried out with an oxidizing agent in the presence of (1) N-oxyl compound and (2) bromide, iodide or mixtures thereof. As the N-oxyl compound used for oxidizing the cellulosic raw material, any compound can be used as long as it promotes the target oxidation reaction. For example, examples of the N-oxyl compound used in the present invention include 2,2,6,6-tetramethyl-1-piperidine-N-oxy radical (hereinafter also referred to as “TEMPO”), 4-hydroxy-2, A compound that generates a 2,6,6-tetramethyl-1-piperidine-N-oxy radical (hereinafter also referred to as “4-hydroxy TEMPO”) is preferable. Moreover, the derivative | guide_body obtained from TEMPO or 4-hydroxy TEMPO can also be used, and the derivative | guide_body of 4-hydroxy TEMPO is the most preferable especially. The 4-hydroxy TEMPO derivative is a derivative obtained by etherifying the hydroxyl group of 4-hydroxy TEMPO with an alcohol having a linear or branched carbon chain having 4 or less carbon atoms, or obtained by esterification with a carboxylic acid or a sulfonic acid. The derivatives are preferred. When 4-hydroxy TEMPO is etherified, if an alcohol having 4 or less carbon atoms is used, the resulting derivative becomes water-soluble regardless of the presence or absence of a saturated or unsaturated bond in the alcohol, making it an excellent oxidation catalyst. A functional 4-hydroxy TEMPO derivative can be obtained. Furthermore, an azaadamantane type nitroxy radical is also preferable because it can produce uniform CNF in a short time.

  The amount of the N-oxyl compound such as TEMPO or 4-hydroxy TEMPO derivative used for oxidizing the cellulosic raw material is not particularly limited as long as it is a catalytic amount capable of converting the cellulosic raw material into nanofibers. For example, it is about 0.01 to 10 mmol, preferably about 0.05 to 5 mmol, with respect to 1 g of cellulosic raw material.

  As the bromide or iodide used for oxidation of the cellulose-based raw material, a compound that can be dissociated and ionized in water, such as an alkali metal bromide or an alkali metal iodide, can be used. The amount of bromide or iodide used can be selected as long as the oxidation reaction can be promoted. For example, it is 0.1 to 100 mmol, preferably 0.1 to 10 mmol, and more preferably about 0.5 to 5 mmol with respect to 1 g of cellulosic raw material.

  Oxidizing agents that can promote the desired oxidation reaction, such as halogens, hypohalous acids, halous acids, perhalogen acids or their salts, halogen oxides, peroxides, etc. Any oxidizing agent can be used. Among these, from the viewpoint of production cost, sodium hypochlorite, which is most widely used in industrial processes at present and is low in environmental load, is particularly preferable. The amount of the oxidizing agent used can be selected within a range that can promote the oxidation reaction. For example, it is about 0.5 to 500 mmol, preferably 0.5 to 50 mmol, and more preferably about 2.5 to 25 mmol with respect to 1 g of cellulosic raw material.

  As described above, the oxidation of the cellulose-based raw material in the present invention is carried out by (1) a compound selected from the group consisting of N-oxyl compounds such as 4-hydroxy TEMPO derivatives and (2) bromide, iodide, and mixtures thereof. In the presence, it is preferably carried out in water using an oxidizing agent such as sodium hypochlorite. In this method, since the oxidation reaction of the cellulosic raw material can proceed smoothly and efficiently even under mild conditions, the reaction temperature may be about 15 to 30 ° C. As the reaction progresses, a carboxyl group is generated in the cellulose, so a decrease in the pH of the reaction solution is observed, but in order to advance the oxidation reaction efficiently, an alkaline solution such as an aqueous sodium hydroxide solution is added to react. It is desirable to maintain the pH of the liquid at 9 to 12, preferably 10 to 11.

The amount of carboxyl groups in the oxidized cellulose is preferably 0.5 mmol / g or more, more preferably 0.9 mmol / g or more, and further preferably 1.2 mmol / g or more with respect to 1 g of cellulose dry. The upper limit is about 2.2 mmol or less, preferably 2.0 mmol or less, and more preferably 1.8 mmol or less. The carboxyl group amount was adjusted to 60 by preparing 60 mL of a 0.5 wt% slurry of cellulose and adding 0.1 M hydrochloric acid aqueous solution to pH 2.5, then dropping 0.05 N sodium hydroxide aqueous solution dropwise to adjust the pH to 11. The electric conductivity is measured until it is, and it can be calculated from the amount of sodium hydroxide (a) consumed in the neutralization step of the weak acid where the change in electric conductivity is slow, using the following equation.
Carboxyl group amount (mmol / g pulp) = a (mL) × 0.05 / cellulose weight (g)

3) Etherification (carboxymethylation)
Etherification can be carried out by mercerizing a cellulose raw material as a bottoming raw material and then etherifying. Usually, a solvent is used for the reaction. Examples of the solvent include water, alcohol (for example, lower alcohol), and a mixed solvent thereof. Examples of the lower alcohol include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, isobutanol, and tertiary butanol. The mixing ratio of the lower alcohol in the mixed solvent is usually 60% by weight or more or 95% by weight or less, and preferably 60 to 95% by weight. The amount of the solvent is usually 3 times the weight of the cellulose raw material. Although the upper limit of the amount is not particularly limited, it is 20 times by weight. Therefore, the amount of the solvent is preferably 3 to 20 times by weight.

  Mercerization is usually performed by mixing a bottoming raw material and a mercerizing agent. Examples of mercerizing agents include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. The amount of the mercerizing agent used is preferably 0.5 times mol or more, more preferably 1.0 mol or more, and further preferably 1.5 times mol or more per anhydroglucose residue of the starting material. The upper limit of the amount is usually 20 times mol or less, preferably 10 times mol or less, more preferably 5 times mol or less. Therefore, the amount of mercerizing agent used is preferably 0.5 to 20 times mol, and 1. 0-10 times mole is more preferable, and 1.5-5 times mole is further more preferable.

  The mercerization reaction temperature is usually 0 ° C. or higher, preferably 10 ° C. or higher, and the upper limit is usually 70 ° C. or lower, preferably 60 ° C. or lower. Therefore, the reaction temperature is usually 0 to 70 ° C, preferably 10 to 60 ° C. The reaction time is usually 15 minutes or longer, preferably 30 minutes or longer. The upper limit of the time is usually 8 hours or less, preferably 7 hours or less. Therefore, the reaction time is usually 15 minutes to 8 hours, preferably 30 minutes to 7 hours.

  The etherification reaction is usually performed by adding a carboxymethylating agent to the reaction system after mercerization. Examples of the carboxymethylating agent include sodium monochloroacetate. The addition amount of the carboxymethylating agent is usually preferably 0.05 times mol or more, more preferably 0.5 times mol or more, and further preferably 0.8 times mol or more per glucose residue of the cellulose raw material. The upper limit of the amount is usually 10.0 times mol or less, preferably 5 mol or less, more preferably 3 times mol or less, and therefore the amount is preferably 0.05 to 10.0 times mol, more Preferably it is 0.5-5 times mole, More preferably, it is 0.8-3 times mole. The reaction temperature is usually 30 ° C. or higher, preferably 40 ° C. or higher, and the upper limit is usually 90 ° C. or lower, preferably 80 ° C. or lower. Accordingly, the reaction temperature is usually 30 to 90 ° C, preferably 40 to 80 ° C. The reaction time is usually 30 minutes or longer, preferably 1 hour or longer, and the upper limit is usually 10 hours or shorter, preferably 4 hours or shorter. Therefore, the reaction time is usually 30 minutes to 10 hours, preferably 1 hour to 4 hours. The reaction solution may be stirred as necessary during the carboxymethylation reaction.

  The degree of carboxymethyl substitution per anhydroglucose unit in carboxymethylated cellulose is preferably 0.01 or more, more preferably 0.05 or more, and further preferably 0.10 or more. The upper limit of the degree of substitution is preferably 0.50 or less, more preferably 0.40 or less, and still more preferably 0.35 or less. Accordingly, the degree of carboxymethyl group substitution is preferably from 0.01 to 0.50, more preferably from 0.05 to 0.40, and even more preferably from 0.10 to 0.30.

Measurement of the degree of carboxymethyl substitution per glucose unit of carboxymethylated cellulose is, for example, by the following method. That is, 1) About 2.0 g of carboxymethylated cellulose (absolutely dry) is precisely weighed and put into a 300 mL conical stoppered Erlenmeyer flask. 2) Add 100 mL of a solution obtained by adding 100 mL of special grade concentrated nitric acid to 1000 mL of nitric acid methanol and shake for 3 hours to convert the carboxymethylcellulose salt (carboxymethylated cellulose) to hydrogen-type carboxymethylated cellulose. 3) 1.5-2.0 g of hydrogen-type carboxymethylated cellulose (absolutely dry) is precisely weighed and placed in a 300 mL Erlenmeyer flask with a stopper. 4) Wet the hydrogen-type carboxymethylated cellulose with 15 mL of 80% methanol, add 100 mL of 0.1N NaOH, and shake at room temperature for 3 hours. 5) Back titrate excess NaOH with 0.1N H ₂ SO ₄ using phenolphthalein as indicator. 6) The degree of carboxymethyl substitution (DS) is calculated by the following formula:
A = [(100 × F ′ − (0.1 N H ₂ SO ₄ ) (mL) × F) × 0.1] / (absolute dry weight of hydrogen-type carboxymethylated cellulose (g))
DS = 0.162 × A / (1-0.058 × A)
A: 1N NaOH amount (mL) required for neutralizing 1 g of hydrogen-type carboxymethylated cellulose
F: Factor of 0.1N H ₂ SO ₄ F ′: Factor of 0.1N NaOH

4) Defibration CNF can be manufactured by carrying out the wet atomization process and defibrating the cellulose raw material chemically modified in this way. As the wet atomization treatment, for example, mixing, stirring, emulsifying, and dispersing devices such as a high-speed shear mixer and a high-pressure homogenizer can be used alone or in combination of two or more. In particular, CNF can be efficiently produced by performing wet atomization using an ultra-high pressure homogenizer capable of applying a pressure of 100 MPa or more, preferably 120 MPa or more, and more preferably 140 MPa or more.

  The amount of carboxyl groups in CNF is the same as the amount of carboxyl groups in oxidized cellulose that is a raw material. The degree of carboxymethyl substitution of CNF is also the same as the degree of carboxymethyl substitution of the carboxymethylated cellulose that is the raw material.

5) Pulp mixed with CNF The freeness (csf) of the pulp mixed with CNF is not limited, but is preferably 0 to 600 mL. When the pulp is used for paperboard, the lower limit of the freeness (csf) is preferably 50 mL or more. When the pulp is used for paper (other than paperboard), the upper limit of the freeness (csf) is preferably 500 mL or less. If the pulp freeness is too low, water drainage during paper making is poor, the speed of paper making does not increase, and problems such as deterioration of the resulting paper may occur. More preferably, it is more preferably 200 mL or more.

(3) a basis weight of CNF containing paper characteristics present invention is preferably from 10 to 500 g / ^{m 2,} and more preferably 20~260g / ^{m 2.} The paper thickness is preferably 10 to 1000 μm. The basis weight of CNF containing paperboard of the present invention is preferably from 90~1600g / ^{m 2,} and more preferably 150~900g / ^{m 2.} The total thickness of each layer of the multilayer paper is preferably about 100 to 1700 μm, and preferably 150 to 1000 μm.

  The CNF-containing paper or paperboard of the present invention is excellent in formation. Formation is the uniformity of fiber distribution in the paper. The formation can be measured by the light transmission variation method. The light transmitted light variation method is a method for measuring the in-plane distribution of the transmitted light amount of a sample. Specifically, 1) irradiate the sample with light, obtain an image obtained by the transmitted light, 2) divide the image into several cells, measure the gray level of each cell, 4) It is preferable that the gray level standard deviation is calculated, and 5) it is evaluated by the formation index obtained from the standard deviation. The formation index is a parameter representing the goodness of formation, and the lower the value, the better the formation. In the case of paper, the formation can be measured by using paper that has been made, and in the case of paperboard, the formation can be measured after dividing each layer of the multilayer paper. Paper or paperboard containing a large amount of CNF tends to deteriorate the formation due to poor dehydration, pulp flocculation, etc. However, the paper or paperboard of the present invention has a small amount of CNF added, so it deteriorates the formation. The effect of improving the paper strength of CNF can be obtained.

  The CNF-containing paper or paperboard of the present invention has excellent strength despite containing waste paper pulp. The reason for this is not limited, but it is assumed that a lot of fine fibers contained in the waste paper pulp remain in the paper due to CNF and the bond between fibers becomes strong.

  The CNF-containing paper or paperboard of the present invention may be provided with a clear coating layer or a pigment coating layer by a known method.

2. Method for Producing CNF-Containing Paper or Paperboard The CNF-containing paper or paperboard of the present invention can be produced by mixing CNF with pulp slurry (paper material) and making paper using the sample. A known paper machine such as a long net paper machine, a twin wire paper machine, or a circular net type paper machine can be used for paper making, and the paper making conditions are not limited. In the present invention, waste paper pulp of 20% by weight or more in the total pulp is used as essential, but in addition to this, chemical pulp (coniferous bleached kraft pulp (NBKP) or unbleached kraft pulp (NUKP), hardwood bleached kraft pulp (LBKP) Or unbleached kraft pulp (LUKP), etc.), mechanical pulp (grand pulp (GP), thermomechanical pulp (TMP), chemithermomechanical pulp (CTMP), etc.) can be used alone or mixed in any proportion. Also good. In the paper or paperboard of the present invention, it is preferable to contain used paper pulp and CNF in the same paper layer. In the case of paperboard, it is preferable that any paper layer contains the used paper pulp and CNF. The pH during papermaking may be acidic, neutral, or alkaline. The pulp slurry has a high yield during papermaking. The reason for this is not limited, but it is presumed that many fine fibers in the waste paper pulp are retained in the paper by CNF as described above.

  The CNF-containing paper or board may contain a filler. Examples of the filler include known fillers such as white carbon, talc, kaolin, clay, heavy calcium carbonate, light calcium carbonate, titanium oxide, synthetic resin filler, and carry-in filler derived from waste paper. Among these, from the viewpoints of the environment and the storage stability of paper, it is desirable to use calcium carbonate to make neutral papermaking so that the paper surface has a pH of 6-9.

  Furthermore, the CNF-containing paper or paperboard contains a sulfuric acid band, a sizing agent, a paper strength enhancer, a yield improver, a drainage improver, a colorant, a dye, an antifoaming agent, a bulking agent, and the like as necessary. Also good. Moreover, as above-mentioned, a clear coating layer or a pigment coating layer can also be provided on a CNF containing paper or paperboard by a well-known method.

3. Uses The use of the CNF-containing paper or paperboard of the present invention is not limited, for example, various printing papers such as offset printing, gravure printing, inkjet printing, wet or dry electrophotographic printing, various information papers such as pressure sensitive paper, thermal paper, It can be used for newsprint paper, wrapping paper, postcard paper, cardboard base paper such as liner and core base paper, paperboard base paper, white paperboard and household paper.

[Example 1]
(1) Manufacture of CNF Bleached unbeaten kraft pulp derived from conifers (whiteness 85%: Nippon Paper Industries Co., Ltd.) 5.00 g (absolutely dried) TEMPO (produced by Sigma Aldrich) 39 mg (absolutely dried 1 g of cellulose) The solution was added to 500 mL of an aqueous solution in which 0.05 mmol) and 514 mg of sodium bromide (1.0 mmol with respect to 1 g of completely dry cellulose) were dissolved, and stirred until the pulp was uniformly dispersed. An aqueous sodium hypochlorite solution was added to the reaction system so that sodium hypochlorite was 5.5 mmol / g, and the oxidation reaction was started at room temperature. During the reaction, the pH in the system was lowered, but a 3M sodium hydroxide aqueous solution was sequentially added to adjust the pH to 10. The reaction was terminated when sodium hypochlorite was consumed and the pH in the system no longer changed. The reaction mixture was filtered through a glass filter to separate the pulp, and the pulp was sufficiently washed with water to obtain oxidized pulp (carboxylated cellulose). The pulp yield was 90%, the time required for the oxidation reaction was 90 minutes, and the amount of carboxyl groups was 1.6 mmol / g. This was adjusted to 0.55% (w / v) with water and treated three times with an ultra-high pressure homogenizer (20 ° C., 150 MPa) to obtain an aqueous dispersion of oxidized cellulose nanofibers. The average fiber diameter of the oxidized cellulose nanofiber (hereinafter also referred to as “TEMPO-CNF”) was 3 nm, and the aspect ratio was 250.

(2) Manufacture of CNF-containing paper Undeinked waste paper pulp (manufactured by Nippon Paper Industries Co., Ltd.) derived from magazine waste paper is stirred at a speed of 500 rpm with a three-one motor, and 1.5% by weight with respect to 100% by weight of pulp. (Solid content) sulfuric acid band, 0.025 wt% polyethyleneimine, TEMPO-CNF, 0.6 wt% polyacrylamide as paper strength agent, 0.2 wt% sizing agent were added in order, and the pulp slurry was Prepared. The amount of TEMPO-CNF added was 10 ppm with respect to the dry weight of waste paper pulp. The freeness (csf) of the CNF-containing pulp was 360 mL. After adjusting the concentration of the slurry, single layer paper was produced using a paper machine. The basis weight was 27.7 g / m ² . The paper was evaluated. The results are shown in Table 1.

[Example 2]
A paper was produced and evaluated in the same manner as in Example 1 except that the amount of CNF was 1000 ppm.

[Comparative Example 1]
A paper was manufactured and evaluated in the same manner as in Example 1 except that CNF was not added. The results are shown in Table 1.

[Example 3]
Paper in the same manner as in Example 1 except that deinked waste paper pulp derived from newspaper waste paper (Csf 210 mL, manufactured by Nippon Paper Industries Co., Ltd.) was used instead of undeinked waste paper pulp derived from magazine waste paper. Were manufactured and evaluated.

[Examples 4 and 5]
A paper was produced and evaluated in the same manner as in Example 3 except that the amount of TEMPO-CNF was changed to 1000 ppm and 10,000 ppm.

[Example 6]
To a stirrer that can mix pulp, 200 g dry pulp (NBKP (conifer bleached kraft pulp), manufactured by Nippon Paper Industries Co., Ltd.) and 111 g sodium hydroxide dry weight are added, resulting in a pulp solid content of 20% by weight. Water was added so that Then, after this mixture was stirred at 30 ° C. for 30 minutes, 216 g of sodium monochloroacetate (in terms of active ingredient) was added. The mixture was stirred for 30 minutes, then heated to 70 ° C. and further stirred for 1 hour. Thereafter, the reaction product was taken out, neutralized, and washed to obtain a carboxymethylated pulp having a carboxymethyl substitution degree of 0.25 per glucose unit. Thereafter, water was added to the carboxymethylated pulp to dilute the solid content concentration to 1% by weight, and it was treated five times with a high-pressure homogenizer (treatment pressure 150 MPa) to obtain C-converted CNF. The obtained fiber had an average fiber diameter of 15 nm and an aspect ratio of 50. A paper was produced and evaluated in the same manner as in Example 4 except that the CCM CNF was used instead of TEMPO-CNF.

[Comparative Example 2]
A paper was produced and evaluated in the same manner as in Example 3 except that CNF was not added. The results are shown in Table 1.

[Comparative Examples 3 and 4]
Paper was produced and evaluated in the same manner as in Comparative Example 1 and Example 2 except that LBKP (Nippon Paper Industries Co., Ltd., 420 mL) was used instead of undeinked waste paper pulp derived from magazine waste paper.

[Example 7]
50% by weight of deinked waste paper pulp (manufactured by Nippon Paper Industries Co., Ltd.) and 50% by weight of LBKP (manufactured by Nippon Paper Industries Co., Ltd.) from newspaper waste paper are stirred at a speed of 500 rpm by a three-one motor, and 100% by weight of the pulp 1.5 wt% (solid content) sulfuric acid band, 0.025 wt% polyethyleneimine, TEMPO-CNF prepared in Example 1, 0.6 wt% polyacrylamide as a paper strength agent, A pulp slurry was prepared by sequentially adding 2% by weight of a sizing agent. The amount of TEMPO-CNF added was 1000 ppm based on the dry weight of waste paper pulp. After adjusting the concentration of the slurry, single layer paper was produced using a paper machine. The basis weight was 38.4 g / m ² . The paper was evaluated. The results are shown in Table 1.

[Comparative Example 5]
A paper was produced and evaluated in the same manner as in Example 7 except that CNF was not added. The results are shown in Table 1.

[Evaluation methods]
(1) Basis weight: measured based on JIS P 8223.
(2) Thickness: Measured according to JIS P 8118.
(3) Density: The density was determined from the basis weight and thickness measured in the above (1) and (2) with reference to JIS P 8118.
(4) Ash content: Measured according to JIS P 8251: 2003.
(5) Tensile strength: measured according to JIS P8113 (6) Breaking length: measured according to JIS P81113: 1998
(7) Tensile stiffness: Measured using a tensile strength measuring instrument sEO62 / 064 manufactured by Lorentzen & Wettre.
(8) Geographic index: Measured using a formation tester “FMT-MIII” manufactured by Nomura Corporation. The formation shows that the lower the value, the better.

  The paper of the present invention is superior in strength compared to conventional paper.

Claims (7)

Containing 20% by weight or more of waste paper pulp,
Paper or paperboard, wherein at least one paper layer contains 3 to 10,000 ppm by weight of cellulose nanofibers relative to the pulp of the paper layer.   The paper or paperboard of Claim 1 whose said cellulose nanofiber is carboxylated cellulose nanofiber.   The paper or paperboard of Claim 1 or 2 whose said cellulose nanofiber is the carboxylated cellulose nanofiber obtained by the oxidation using an N-oxyl compound.   The paper or paperboard of Claim 1 whose said cellulose nanofiber is a carboxymethylated cellulose nanofiber.   The paper or paperboard according to any one of claims 1 to 4, wherein the waste paper pulp is selected from the group consisting of undeinked waste paper pulp, deinked waste paper pulp, and combinations thereof.   The paper or paperboard in any one of Claims 1-5 whose said waste paper pulp is a magazine waste paper pulp. A method for producing the paper or paperboard according to any one of claims 1 to 6,
A method for producing paper or paperboard, comprising a step of papermaking a pulp slurry containing waste paper pulp and cellulose nanofibers.